The present invention relates to a primer composition comprising a saturated hydrocarbon polymer having at least one silicon-containing group which has hydroxyl group or hydrolyzable group bound to the silicon atom and is capable of crosslinking under formation of a siloxane bond (hereinafter referred to as xe2x80x9creactive silicon groupxe2x80x9d) and to a method of effecting adhesion for sealing compositions using the same.
In recent years, elastic sealing compositions have been used widely in buildings, motor vehicles and so on. Sealing compositions are materials used for the purpose of filling up junctions or gaps between various parts and providing airtightness and watertightness. Therefore, they are required to show good adhesive properties for various substrates constituting joints, window frames and the like, namely inorganic materials such as glass, ceramics, metals, cement, mortar, etc., or organic materials such as plastics (hereinafter collectively referred to as xe2x80x9csubstratesxe2x80x9d). However, the adhesive properties of sealing compositions are still unsatisfactory and, therefore, the use of primers is essential in many cases.
On the other hand, silicone-based, modified silicone-based, polysulfide-based and polyurethane-based sealing compositions are well known as compositions to be applied to joints of the interior and exterior of general buildings. These sealing compositions are used properly based on the policy of xe2x80x9cthe right thing in the right placexe2x80x9d. Namely, suitable sealing compositions are selected according to the joints (inclusive of substrate species) to be sealed. Thus, exclusive-use primers adapted to respective sealing compositions have been developed.
As regards primers for sealing compositions for buildings, urethane-based primers containing an isocyanate prepolymer as a main component, and silane type primers constituted of a low-molecular-weight silane compound such as a silane coupling agent, or an organopolysiloxane, among others, are commercially available. However, it is a problem that even when these primers are used, the weather resistance and water resistance of the adhesion are not satisfactory and the effects of the primers cannot be produced over a prolonged period of time.
On the other hand, sealing compositions containing, as the main component thereof, a saturated hydrocarbon polymer containing a reactive silicon group (in particular isobutylene-based sealing compositions with an isobutylene-based polymer as the main chain skeleton) have recently been developed. These isobutylene-based sealing compositions are characterized in that they are excellent in dynamic follow properties, heat resistance, weather resistance, water resistance and coatability and do not contaminate joint surroundings. Their performance characteristics are thus suited for their use as universal sealing compositions. However, no exclusive-use primers for isobutylene-based sealing compositions have ever been developed.
The present invention has its object to provide a primer composition excellent in adhesion properties to various substrates, in particular a primer composition for effecting good adhesion, to various substrates, of sealing compositions containing, as a Main component, a saturated hydrocarbon polymer having at least one reactive silicon group, as well as a method of effecting adhesion.
The present inventors made intensive investigations in an attempt to solve such problems and, as a result, found that the above object can be accomplished by providing a primer composition containing a saturated hydrocarbon polymer having at least one reactive silicon group. The present invention has now been completed based on such findings.
The present invention thus relates to a primer composition which comprises (A) a saturated hydrocarbon polymer having at least one silicon-containing group which has hydroxyl group or hydrolyzable group bound to the silicon atom and is capable of crosslinking under formation of a siloxane bond, in particular to a primer composition which comprises 0.1 to 10,000 parts by weight of (B) a silane coupling agent per 100 parts by weight of the (A) saturated hydrocarbon polymer having at least one silicon-containing group which has hydroxyl group or hydrolyzable group bound to the silicon atom and is capable of crosslinking under formation of a siloxane bond.
The present invention is now described in detail.
The saturated hydrocarbon polymer having at least one reactive silicon group, namely component (A), to be used in the present invention is a component characterizing the present invention. It shows good adhesion to various substrates such as glass and metals and functions as a component forming films excellent in resistance to weather through glass and in water resistance. Thus, it is a component providing the primer composition of the present specification with strong adhesion and durability.
This saturated hydrocarbon polymer having at least one reactive silicon group, namely component (A), is a polymer substantially free of carbon-carbon unsaturated bonds other than aromatic ring bonds. As such, there may be mentioned, for example, polyethylene, polypropylene, polyisobutylene, hydrogenated polybutadiene and hydrogenated polyisoprene.
The reactive silicon group is typically a group represented by the general formula (1) 
wherein R1 and R2 each independently is a hydrogen atom, an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms, an aralkyl group containing 7 to 20 carbon atoms or a triorganosiloxy group of the formula (Rxe2x80x2)3SiOxe2x80x94 (in which each Rxe2x80x2 independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group containing 1 to 20 carbon atoms), each X independently represents a hydroxyl group or a hydrolyzable group, a is 0, 1, 2 or 3, b is 0, 1 or 2, to the exclusion of the case where a and b are simultaneously 0 (zero), and m is 0 (zero) or an integer of 1 to 19.
As the hydrolyzable group, there may be mentioned, for example, a hydrogen atom and groups commonly used for the same purposes, such as alkoxy, acyloxy, ketoximate, amino, amido, aminoxy, mercapto and alkenyloxy groups.
Among these, alkoxy, amido, aminoxy groups are preferred and alkoxy groups are most preferred because of their mild hydrolyzability and ease of handling.
One to three hydrolyzable or hydroxyl groups can be bound to one silicon atom and the sum (a+xcexa3b) is preferably within the range of 1 to 5. When two or more hydrolyzable or hydroxyl groups are bound in the reactive silicon group, they may be the same or different.
The number of silicon atoms constituting the reactive silicon group is one or more. When silicon atoms are connected via siloxane bonding, the number thereof is preferably not more than 20.
In particular, reactive silicon groups represented by the general formula (2) 
wherein R2, X and a are as defined above, are readily available, hence preferred.
The number of reactive silicon groups per molecule of the (A) saturated hydrocarbon polymer is not less than 1, preferably 1.1 to 5. When the number of reactive silicon groups per molecule is below 1, the curability will be insufficient and thereby good coats may not be obtained in some instances.
The reactive silicon group or groups may occur at one or both ends of and/or within the molecular chain of the saturated hydrocarbon polymer. In particular, when the reactive silicon group or groups occur at one or both ends of the molecular chain, the amount of those effective network chains of the saturated hydrocarbon polymer component contained in the finally formed cured coats increases, therefore those are preferred owing to making it easy to obtain high-strength coats.
These saturated hydrocarbon polymers having at least one reactive silicon group, namely component (A), may be used either singly or in combination.
The polymer constituting the (A) saturated hydrocarbon polymer having at least one reactive silicon group to be used in the present invention can be obtained by (1) polymerizing an olefinic compound containing 1 to 6 carbon atoms, such as ethylene, propylene, 1-butene or isobutylene, as a main monomer, or (2) homopolymerizing a diene compound, such as butadiene or isoprene, or copolymerizing such diene compound with such an olefinic compound as mentioned above, and then hydrogenating the resulting polymer or copolymer. Isobutylene polymers and hydrogenated polybutadiene polymers are preferred, however, since functional group introduction thereinto at one or both ends of the molecular chain can be easily realized, their molecular weights can be easily controlled, and the number of terminal functional groups can be increased.
As regards the isobutylene polymers, the monomer units thereof may be composed of isobutylene units alone, or may contain monomer units copolymerizable with isobutylene preferably in an amount not more than 50% (% by weight; hereinafter the same shall apply), more preferably not more than 30%, most preferably not more than 10% of the isobutylene polymers.
As such monomer constituent, there may be mentioned olefins containing 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinylsilanes, allylsilanes and the like. As such copolymer constituents, there may be mentioned, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, xcex1-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, xcex2-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyl-disiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, xcex3-methacryloyloxypropyltrimethoxysilane, xcex3-methacryloyloxypropylmethyldimethoxysilane and the like.
When a vinylsilane or an allylsilane is used as the monomer copolymerizable with isobutylene, a silicon content, hence an increased amount of groups capable of acting as silane coupling agents is increased, with the result that the adhesion properties of the resulting primer composition is improved.
Like the case of the above-mentioned isobutylene polymers, the hydrogenated polybutadiene polymers and other saturated hydrocarbon polymers may contain other monomer units in addition to the main component monomer units.
The (A) saturated hydrocarbon polymer having at least one reactive silicon group to be used in the present invention may contain a small proportion, preferably not more than 10%, more preferably not more than 5%, most preferably not more than 1%, of monomer units, for example a polyene compound such as butadiene or isoprene, leaving a double bond after polymerization up to the limit allowing accomplishment of the objects of the present invention.
The (A) saturated hydrocarbon polymer having at least one reactive silicon group, preferably an isobutylene polymer or hydrogenated polybutadiene polymer preferably has a number average molecular weight of about 500 to 50,000. In particular, those liquid or flowable ones which have a molecular weight of about 1,000 to 20,000 are preferred from the ease-of-handle viewpoint, among others.
Hereinafter, the methods of preparing the (A) saturated hydrocarbon polymer having at least one reactive silicon group are described using isobutylene polymer having at least one reactive silicon group as an example.
Among isobutylene polymers having at least one reactive silicon group, those isobutylene polymers having a reactive silicon group at one or both ends of the molecular chain can be prepared by using a terminal function type isobutylene polymer, preferably one having functional groups at both ends, obtained by the polymerization method called inifer method (cationic polymerization method using a specific compound called inifer which serves as an initiator and also as a chain transfer agent). Thus, for example, a polyisobutylene having a terminal unsaturated group or groups is obtained by the hydrogen halide elimination reaction of said polymer or by the reaction for introducing an unsaturated group into a polymer as described in Japanese Kokai Publication Sho-63-105005 and, then, the terminally unsaturated polyisobutylene is subjected to the addition reaction called hydrosilylation using a hydrosilane compound represented by the general formula 
wherein R1, R2, X, a, b and m are as defined above (this compound is a compound resulting from binding of a hydrogen atom to a group of general formula (1)), preferably a hydrosilane compound represented by the general formula 
wherein R2, X and a are as defined above, in the presence of a platinum catalyst to thereby introduce the reactive silicon group into the polymer. The hydrosilane compound includes, but is not limited to, halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and phenyldichlorosilane; alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane and phenyldimethoxysilane; acyloxysilanes such as methyldiacatoxysilane and phenyldiacetoxysilane: ketoximatosilanes such as bis(dimethylketoximato)methylsilane and bis(cyclohexylketoximato)methylsilane, for instance. Among these, halogenated silanes and alkoxysilanes are preferred.
Such production methods are described, for example in Japanese Kokoku Publication Hei-04-69659, Japanese Kokoku Publication Hei-07-108928, Japanese Patent No. 2512468, Japanese Kokai Publication Sho-64-22904, Japanese Patent No. 2539445 and elsewhere.
Isobutylene polymers having a reactive silicon group or groups within the molecular chain are prepared by adding a vinylsilane or allylsilane each having the reactive silicon group to a monomer composition mainly containing isobutylene and copolymerizing said composition.
Further, isobutylene polymers having reactive silicon groups at one or both ends of the molecular chain and within the molecular chain are produced by copolymerizing, on the occasion of the polymerization for preparing isobutylene polymers having a reactive silicon group or groups at one or both ends of the molecular chain, vinylsilane or allylsilane each having a reactive silicon group in addition to the main component isobutylene monomer and then introducing a reactive silicon group into the resulting polymers at one or both ends of the molecular chain.
As the vinylsilane or allylsilane each having the reactive silicon group, there may be mentioned, for example, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, xcex3-methacryloyloxypropyltrimethoxysilane, xcex3-methacryloyloxypropylmethyldimethoxysilane and the like.
As regards the hydrogenated polybutadiene polymers mentioned above, a hydrogenated polybutadiene polymer having a terminal olefinic group (hereinafter, olefin-terminated hydrogenated polybutadiene polymer) is prepared, for example, by first converting the hydroxyl group or groups of a hydroxyl-terminated hydrogenated polybutadiene polymer to oxymetal groups such as xe2x80x94ONa or xe2x80x94OK and then reacting the same with an organohalogen compound represented by the general formula (3)
CH2xe2x95x90CHxe2x80x94R3xe2x80x94Yxe2x80x83xe2x80x83(3)xe2x80x94 
wherein Y is a halogen atom, such as a chlorine or iodine atom and R3 is a divalent organic group of the formula xe2x80x94R4xe2x80x94, xe2x80x94R4xe2x80x94OCO or xe2x80x94R4xe2x80x94COxe2x80x94 (in which R4 is a divalent hydrocarbon group containing 1 to 20 carbon atoms, preferably an alkylene, cycloalkylene, arylene or aralkylene group) and most preferably is a divalent group selected from among xe2x80x94CH2xe2x80x94 and xe2x80x94Rxe2x80x3xe2x80x94C6H5xe2x80x94CH2xe2x80x94 (in which Rxe2x80x3 is a hydrocarbon group containing 1 to 10 carbon atoms).
As the method of converting the terminal hydroxyl group of the hydroxyl-terminated hydrogenated polybutadiene polymer to an oxymetal group, there may be mentioned the method comprising reacting the terminal hydroxyl group with an alkali metal such as Na or K, a metal hydride such as NaH, a metal alkoxide such as NaOCH3, an alkali hydroxide such as NaOH or KOH, or the like.
The above-mentioned methods give olefin-terminated hydrogenated polybutadiene polymer having approximately the same molecular weight as that of the hydroxyl-terminated hydrogenated polybutadiene polymer used as the starting material. When polymers having a higher molecular weight are desired, the molecular weight can be increased by reacting with a polyvalent organohalogen compound containing two or more halogen atoms per molecule, for example methylene chloride, bis(chloromethyl)benzene or bis(chloromethyl)ether, prior to the reaction with the organohalogen compound of general formula (3). Hydrogenated polybutadiene polymers having a higher molecular weight and a terminal olefinic group can be obtained by the subsequent reaction with the organohalogen compound of general formula (3).
The above-mentioned organohalogen compound represented by the general formula (3) includes as typical examples thereof, but is not limited to, allyl chloride, allyl bromide, vinyl(chloromethyl)benzene, allyl(chloromethyl)benzene, allyl(bromomethyl)benzene, allyl(chloromethyl)ether, allyl(chloromethoxy)benzene, 1-butenyl(chloromethyl)ether, 1-hexenyl(chloromethoxy)benzene, allyloxy(chloromethyl)-benzene and the like. Among these, allyl chloride is inexpensive and reacts readily, hence is preferred.
The introduction of the reactive silicon group into the above-mentioned olefin-terminated hydrogenated polybutadiene polymer is realized by the addition reaction of a hydrosilane compound using a platinum catalyst, like the case of the isobutylene polymers having a reactive silicon group or groups at one or both ends of the molecular chain.
When the saturated hydrocarbon polymers having at least one reactive silicon group are substantially free of intramolecular unsaturated bonds other than aromatic ring bonds, as mentioned above, the coats formed therefrom can have markedly improved weather resistance as compared with the coats formed from the conventional rubber-like polymers such as unsaturated bond-containing organic polymers or oxyalkylene polymers. Since said polymers are hydrocarbon polymers, they show good moisture shield effects and good water resistance. They form coats which show excellent adhesion properties for various inorganic materials such as glass and aluminum, and have high moisture shielding effects.
The content of the (A) saturated hydrocarbon polymer having at least one reactive silicon group in the primer composition of the present invention is preferably not less than 1%, more preferably not less than 3%, most preferably not less than 5%. In particular, when the primer composition of the present invention is applied to a porous substrate such as mortar, the coats are required to have an increased thickness so that water can be prevented from oozing from the porous material and, therefore, the content of said polymer is preferably not less than 5%, more preferably not less than 10%, most preferably not less than 20%.
The (A) saturated hydrocarbon polymer having at least one reactive silicon group mentioned above is in itself high in viscosity and poor in workability. Therefore, for the purpose of lowering the viscosity of said polymer and improving the handling behavior thereof, various plasticizers may be added in proportions not impairing the adhesion properties or eco-friendly aspect of the primer composition of the present invention.
As plasticizers compatible with the saturated hydrocarbon polymer having at least one reactive silicon group, namely component (A) of the present invention, there may be mentioned polyvinyl oligomers such as polybutene, hydrogenated polybutene, hydrogenated xcex1-olefin oligomers, atactic poly-propylene etc.; aromatic oligomers such as biphenyl, triphenyl, etc.; hydrogenated polyene oligomers such as hydrogenated liquid polybutadiene; paraffin oligomers such as paraffin oil, chlorinated paraffin oil, etc. cycloparaffin oligomers such as naphthene oil etc.; and the like.
Phthalate ester plasticizers, nonaromatic dibasic acid ester plasticizers, phosphate ester plasticizers and the like may also be used in combination with the plasticizers mentioned above, in proportions not lowering the adhesion properties, weather resistance and heat resistance of the primer composition of the present invention. These may be used either singly or in combination.
The plasticizers mentioned above may also be used in lieu of a solvent for adjusting the reaction temperature and the viscosity of the reaction system on the occasion of reactive silicon group introduction into the saturated hydrocarbon polymer.
The addition amount of the above-mentioned plasticizers is preferably 1 to 100 parts (parts by weight; hereinafter the same shall apply), more preferably 10 to 50 parts, per 100 parts of the (A) saturated hydrocarbon group having at least one reactive silicon group. When the addition amount of the plasticizers is lower than said range, the plasticizing effect will be low. At addition amounts higher than said range, sufficient adhesion properties may not be obtained in certain instances.
The silane coupling agent, namely component (B) in the present invention, forms firm coats by reacting with the saturated hydrocarbon polymer having at least one reactive silicon group, namely component (A), and improves the adhesion strength of various sealing compositions such as isobutylene-based sealing compositions or modified silicone-based sealing compositions to various substrates such as glass, metals and mortar. The (B) silane coupling agent is a compound having a silicon atom to which a hydrolyzable group or groups are bound (hereinafter referred to as hydrolyzable silicon group) and having other functional group. As examples of this hydrolyzable silicon group, there may be mentioned those groups in which X is a hydrolyzable group among groups represented by the general formula (1). Specifically, those groups already mentioned hereinabove as hydrolyzable groups may be mentioned here again. From the hydrolysis rate viewpoint, methoxy, ethoxy and the like are preferred. The number of hydrolyzable groups is preferably 2 or more, most preferably 3 or more.
As examples of the functional group other than the hydrolyzable silicon group, there may be mentioned primary, secondary or tertiary amino, mercapto, epoxy, carboxyl, vinyl, isocyanato and isocyanurate groups, halogens and the like. Among these, primary, secondary or tertiary amino, epoxy, isocyanato, isocyanurate and like groups are preferred, and isocyanato and amino groups are most preferred.
As specific examples of the (B) silane coupling agent, there may be mentioned amino-containing silanes such as xcex3-aminopropyltrimethoxysilane, xcex3-aminopropyltriethoxysilane, xcex3-aminopropylmethyldimethoxysilane, xcex3-aminopropylmethyldiethoxysilane, xcex3-(2-aminoethyl)aminopropyltrimethoxysilane, xcex3-(2-aminoethyl)aminopropylmethyldimethoxysilane, xcex3-(2-aminoethyl)aminopropyltriethoxysilane, xcex3-(2-aminoethyl)aminopropylmethyldiethoxysilane, xcex3-ureidopropyltrimethoxysilane, N-phenyl-xcex3-aminopropyltrimethoxysilane, N-benzyl-xcex3-aminopropyltrimethoxysilane and N-vinylbenzyl-xcex3-aminopropyltriethoxysilane; mercapto-containing silanes such as xcex3-mercaptopropyltrimethoxysilane, xcex3-mercaptopropyltriethoxysilane, xcex3-mercaptopropylmethyldimethoxysilane and xcex3-mercaptopropylmethyldiethoxysilane; epoxy-containing silanes such as xcex3-glycidoxypropyltrimethoxysilane, xcex3-glycidoxypropyltriethoxysilane, xcex3-glycidoxypropylmethyldimethoxysilane, xcex2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and xcex2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; carboxysilanes such as xcex2-carboxyethyltriethoxysilane, xcex2-carboxyethylphenylbis(2-methoxyethoxy)silane and N-xcex2-(carboxymethyl)aminoethyl-xcex3-aminopropyltrimethoxysilane; vinyl type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, xcex3-methacryloyloxypropylmethyldimethoxysilane and xcex3-acryloyloxypropylmethyltriethoxysilane; halogen-containing silanes such as xcex3-chloropropyltrimethoxysilane; isocyanurate silanes such as tris(trimethoxysilyl) isocyanurate; isocyanato-containing silanes such as xcex3-isocyanatopropyltrimethoxysilane, xcex3-isocyanatopropyltriethoxysilane, xcex3-isocyanatopropylmethyldiethoxysilane and xcex3-isocyanatopropylmethyldimethoxysilane; and the like. Derivatives which are modifications of these, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, blocked isocyanato-containing silanes, phenylamino long-chain alkylsilanes, aminosilylated silicones and silylated polyesters may also be used as silane coupling agents.
In the present invention, the (B) silane coupling agent is used in an amount of 0.1 to 10,000 parts per 100 parts of the (A) saturated hydrocarbon group having at least one reactive silicon group. In particular, the use thereof in an amount of 1 to 100 parts is preferred. The (B) silane coupling agents mentioned above may be used singly or two or more kinds of them may be used in admixture.
Another tackifier other than the (B) silane coupling agent may be used in the primer composition of the present invention.
The organic titanate ester, namely component (C) in the present invention, is a component for improving the adhesion strength of various sealing compositions, such as isobutylene-based sealing compositions or modified silicone-based sealing compositions, to various substrates, such as glass, metals and mortar. Also, it has another function, namely it improves the adhesive properties at construction joints on the occasion of placing a sealing composition in contact with a cured sealing composition. In particular, it functions so as to improve the adhesion properties at construction joints on the occasion of placing a sealing composition other than a silicone-based sealing composition in contact with a silicone-based sealing composition (earlier placed sealing composition). Further, the (C) organic titanate ester is a component also functioning as a silanol condensation catalyst, promoting the condensation reaction of the reactive silicon groups of the (A) saturated hydrocarbon polymer having at least one reactive silicon group and of the (B) silane coupling agent.
As such organic titanate ester (C), there may be mentioned organic titanate esters, titanium chelate compounds, chelate compounds of titanium with a silicic acid ester, titanate coupling agents, and partial hydrolyzate condensates of these. As specific examples of the organic titanate ester, there may be mentioned tetraisopropyl titanate, tetranormalbutyl titanate, butyl titanate dimer, tetrakis(2-ethylhexyl) titanate, tetrastearyl titanate, tetramethyl titanate, diethoxybis(acetylacetonato)titanium, diisopropylbis(acetylacetonato )titanium, diisopropoxybis(ethyl acetoacetato)titanium, isopropoxy(2-ethyl-1,3-hexanediolato)titanium, di(2-ethylhexoxy)bis(2-ethyl-1,3-hexanediolato)titanium, di-n-butoxybis-(triethanolaminato)titanium, tetraacetylacetonatotitanium, hydroxybis(lactato)titanium, and hydrolyzate condensates of these. As specific examples of the (C) titanate coupling agent, there may be mentioned compounds represented by the formula 
and hydrolyzate condensates of these.
In the present invention, the (C) organic titanate ester is used in an amount of 0.1 to 10,000 parts per 100 parts of the (A) saturated hydrocarbon group having at least one reactive silicon group. In particular, the use thereof in an amount of 1 to 100 parts is preferred. The (C) organic titanate esters mentioned above may be used singly or two or more kinds of them may be used in admixture.
In the primer composition of the present invention, a silanol condensation catalyst may be used as a component (D) functioning to cure the primer composition of the present invention and provide the same with air-drying properties.
As such silanol condensation catalyst (D), there may be mentioned divalent and tetravalent tin-based curing catalysts, aluminum-based curing catalysts, amine-based curing catalysts and the like. Among these, tetravalent tin-based curing catalysts are preferred because of their high catalytic activity. As specific examples of the tetravalent tin-based curing catalysts, there may be mentioned tin carboxylate salts, dialkyltin oxides and compounds represented by the general formula (4)
QdSn(OZ)4-d or [Q2Sn(OZ)]2Oxe2x80x83xe2x80x83(4) 
wherein Q represents a monovalent hydrocarbon group containing 1 to 20 carbon atoms, Z represents a monovalent hydrocarbon group containing 1 to 20 carbon atoms or a functional group capable of forming within itself a coordination bond to Sn, and d is 0, 1, 2 or 3. Reaction products from a tetravalent tin compound such as a dialkyltin oxide, dialkyltin diacetate or the like and a low-molecular-weight silicon compound having one or more hydrolyzable silicon groups, such as tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane or phenyltrimethoxysilane are also useful as curing catalysts markedly accelerating the silanol condensation reaction. Among these, compounds of general formula (4), namely dibutyltin bisacetylacetonate or like chelate compounds or tin alcoholates, are highly active as silanol condensation catalysts and accelerate the film forming reaction rate of the primer composition, hence are more preferred.
As specific examples of the above-mentioned tin carboxylate salts, there may be mentioned dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctoate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin diisooctylmaleate, dibutyltin ditridecylmaleate, dibutyltin dibenzylmaleate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmaleate and dioctyltin diisooctylmaleate.
As specific examples of the above-mentioned dialkyltin oxides, there may be mentioned dibutyltin oxide, dioctyltin oxide, and mixtures of dibutyltin oxide and a phthalate ester.
Specific examples of the above-mentioned chelate compounds include, but are not limited to, 
and the like. Among these, dibutyltin bisacetylacetonate shows a high catalytic activity, is low in cost and is readily available, hence is most preferred.
Specific examples of the above-mentioned tin alcoholates include, but are not limited to, 
and the like. Among these, dialkyltin dialkoxides are preferred. In particular, dibutyltin dimethoxide is low in cost and is readily available, hence is more preferred.
The (D) silanol condensation catalyst other than the tetravalent tin-based curing catalysts mentioned silanol condensation catalysts such as above may also be used. As specific examples, there may be mentioned bivalent tin-based curing catalysts such as stannous octoate; aluminum-based curing catalysts such as aluminum trisacetylacetonate, aluminum tris (ethyl-acetoacetate) and diisopropoxyaluminum ethyl -acetoacetate; zirconium tetraacetylacetonate; lead octoate; amine-based curing catalysts such as butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicyclo(5.4.0)undecene-7 (DBU) or salts of these amine compounds with carboxylic acids; low-molecular-weight polyamide resins obtained from an excess polyamine and a polybasic acid; reaction products from an excess polyamine and an epoxy compound; amino-containing silane coupling agents such as xcex3-aminopropyltrimethoxysilane and N-(xcex2-aminoethyl)aminopropylmethyldimethoxysilane; and, further, other known silanol condensation catalysts such as acidic catalysts and basic catalysts.
These catalysts may be used singly or two or more kinds of them may be used in combination.
The addition amount of this silanol condensation catalyst, namely component (D), is incorporated preferably about 0.1 to 100 parts, more preferably 1 to 20 parts, per 100 parts of the (A) saturated hydrocarbon group having at least one reactive silicon group. When the addition amount of the silanol curing catalyst is below this range, the rate of film formation may become slow and the film formation becomes difficult to achieve in certain instances. Conversely when the addition amount of the (D) silanol curing catalyst exceeds said range, the open time will become too short, which is unfavorable from the workability viewpoint.
In the present invention, a solvent may be used to adjust the primer composition to a viscosity suited for primer application. The solvent may be any one and is not limited to any particular species provided that it can dissolve the components (A) to (D) of the present invention. As specific examples of such solvent, there may be mentioned hydrocarbon solvents such as toluene, xylene, heptane, hexane and petroleum solvents, halogenated solvents such as trichloroethylene, ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, alcohol solvents such as methanol, ethanol and isopropanol, and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. These solvents may be used singly or two or more kinds of them may be used in combination.
The solvent is used preferably in an amount of about 100 to 10,000 parts, more preferably 200 to 2,000 parts, per 100 parts of the (A) saturated hydrocarbon group having at least one reactive silicon group. When the amount of the solvent is below said range, the viscosity of the primer composition will become excessively high, which is unfavorable from the workability viewpoint. When the amount of the solvent exceeds said range, no sufficient adhesion is obtained in some instances.
In the primer composition of the present invention, various antioxidants may be used as necessary. As such antioxidants, there may be mentioned phenolic antioxidants, aromatic amine antioxidants, sulfur-containing hydroperoxide decomposers, phosphorus -containing hydroperoxide decomposers, benzotriazole ultraviolet absorbers, salicylate ultraviolet absorbers, benzophenone ultraviolet absorbers, hindered amine light stabilizers, nickel-containing light stabilizers and the like.
Said phenolic antioxidants include, as specific examples thereof, 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone, n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2xe2x80x2-methylenebis(4-methyl-6-t-butylphenol), 4,4xe2x80x2-butylidenebis(3-methyl-6-t-butylphenol) and 4,4xe2x80x2-thiobis(3-methyl-6-t-butylphenol).
Said aromatic amine antioxidants include, as specific examples thereof, N,Nxe2x80x2-diphenyl-p-phenylenediamine and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline.
Said sulfur-containing hydroperoxide decomposers include, as specific examples thereof, dilauryl 3,3xe2x80x2-thiodipropionate, ditridecyl-3,3xe2x80x2-thiodipropionate and distearyl-3,3xe2x80x2-thiodipropionate.
Said phosphorus-containing hydroperoxide decomposers include, as specific examples thereof, diphenylisooctyl phosphate and triphenylphosphite.
Said benzotriazole ultraviolet absorbers include, as specific examples thereof, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole and 2-(5-methyl-2-hydroxyphenyl)benzotriazole.
Said salicylate ultraviolet absorbers include, as specific examples thereof, 4-t-butylphenyl salicylate and 2,4-di-t-butylphenyl-3,5xe2x80x2-di-t-butyl-4xe2x80x2-hydroxybenzoate.
Said benzophenone ultraviolet absorbers include, as specific examples thereof, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-benzyloxybenzophenone.
Said hindered amine light stabilizers include, as specific examples thereof, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1-{2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl}-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine.
Said nickel-containing light stabilizers include, as specific examples thereof, nickel dibutyldithiocarbamate, [2,2xe2x80x2-thiobis(4-t-octylphenolato)]-2-ethylhexylamine nickel (II) and [2,2xe2x80x2-thiobis(4-t-octylphenolato)]-n-butylamine nickel (II).
These antioxidants may be used singly or two or more kinds of them may be used in combination. As compared with single use, combined use may result in more effective functioning. In particular, the combined use of a phenolic antioxidant, a salicylate ultraviolet absorber and a hindered amine light stabilizer is preferred since the weather resistance of the saturated hydrocarbon polymer having at least one reactive silicon group, namely component (A) is markedly improved by said combined use.
The addition amount of the antioxidants is preferably about 0.1 to 20 parts, more preferably 1 to 10 parts, per 100 parts of component (A). At an addition amount below 0.1 part, the weather resistance cannot be improved sufficiently in some cases whereas, at an addition amount exceeding 20 parts, the cost and adhesion properties of the primer composition will be sacrificed.
Furthermore, weather-resistant property improving agent (compounds having an intramolecular unsaturated group capable of polymerizing upon reaction with oxygen in the air or photopolymerizable substances) may be added, as necessary, to the primer composition of the present invention to further improve the weather-resistant adheasion properties. These can be used singly effectively or may be used in combination.
Said compounds having an intramolecular unsaturated group capable of polymerizing upon reaction with oxygen in the air are, in other words, substances capable of undergoing the oxidative polymerization reaction. Specific examples of the substances capable of undergoing the oxidative polymerization reaction are ester compounds derived from an unsaturated higher fatty acid and an alcohol, diene type polymers or copolymers such as 1,2-polybutadione, 1,4-polybutadiene, and C5-C8 diene, various modifications of said polymers or copolymers (maleinated modifications, boiled oil modifications, etc.) and the like.
As specific examples of said unsaturated higher fatty acid ester compounds, there may be mentioned ester compounds obtained by the condensation reaction between a higher unsaturated fatty acid such as oleic acid, linolic acid, linolenic acid, eleostearic acid, licanic acid, ricinolic acid or arachidonic acid and an alcohol selected from among monohydric alcohols such as methanol and ethanol, dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as trimethylolpropane and glycerol, tetrahydric alcohols such as pentaerythritol, hexahydric alcohols such as sorbitol, organosilicon compounds having a hydroxyl group via an organic group bound to the silicon atom, and the like.
Among these ester compounds, drying oils mainly composed of triglycerides, which are glycerol esters of unsaturated higher fatty acids, for example linseed oil, tung oil, soybean oil, hempseed oil, isano oil, lacquer tree kernel oil, perilla oil, oiticica oil, kaya oil, walnut oil, poppy seed oil, cherry seed oil, pomegranate seed oil, safflower oil, tobacco seed oil, Chinese sumac kernel oil, rubber seed oil, sunflower seed oil, grape kernel oil, balsam seed oil and honewort seed oil, are preferred because of their unexpensiveness and ready availability.
Among said drying oils, those drying oils containing, as main components thereof, triglyceride esters of conjugated unsaturated higher fatty acids such as eleostearic acid, licanic acid, punicic acid, catalpic acid and the like, namely tung oil, oiticica oil, pomegranate seed oil and balsam seed oil and the like are more preferred because of their high weather resistance improving effects.
Said compounds having an intramolecular unsaturated group capable of polymerizing upon reaction with oxygen in the air may be used singly or two or more kinds of them may be used in combination.
Said photopolymerizable substances are, in other words, compounds having an unsaturated group capable of polymerizing as a result of activation of the double bond within the molecule upon light irradiation.
As typical examples of the photopolymerizable unsaturated group contained in said photopolymerizable substances, there may be mentioned vinyl, allyl, vinyl ether group, vinyl thioether group, vinylamino, acetylenically unsaturated groups, acryloyl, methacryloyl, styryl, cinnamoyl and like groups. Among these, acryloyl or methacryloyl are preferred because of their high photoinitiation efficiency.
As examples of said photopolymerizable substances containing an acryloyl or methacryloyl group as the photosensitive group, there may be mentioned acrylamide derivatives, methacrylamide derivatives, (meth)acrylates and the like. Among them, (meth)acrylates are preferred since various kinds of products are readily available. In the present specification, the term xe2x80x9c(meth)acrylatesxe2x80x9d is used to collectively refer to acrylates and methacrylates.
As specific examples of said (meth)acrylate, there may be mentioned propylene (or butylene or ethylene) glycol di(meth)acrylate, which contains two functional groups, trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate, which contain three functional groups, and pentaerythritol tetra(meth)acrylate and dipentaerythritol penta- or hexa(meth)acrylate, which contain four or more functional groups. As specific examples of the oligomer, there may be mentioned oligoesters having a molecular weight of not more than 10,000, such as polyethyleneglycol di(meth)acrylate and polypropyleneglycol di(meth)acrylate. The number of the acrylic or methacrylic type unsaturated groups is preferably not less than 2, more preferably not less than 3. The larger the number of functional groups is, the higher the weather resistant adhesion improving effect of said unsaturated acrylic compound is.
The photopolymerizable substances may be used singly or two or more kinds of them may be used in combination.
The addition amount of the weather-resistant property improving agent is preferably about 0.1 to 100 parts, more preferably 1 to 20 parts, per 100 parts of component (A). When the addition amount is below 0.1 part, the weather resistant adhesion improving effect may be insufficient in certain instances. At an addition amount exceeding 100 parts, the storage stability of the primer composition may be lowered in some instances.
In the primer composition of the present invention, use may be made of various fillers as necessary. As specific examples of said fillers, there may be mentioned woodmeal, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell flour, rice hull flour, graphite, diatomaceous earth, china clay, fumed silica, precipitated silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, aluminum fine powder, flint powder and zinc dust. Among these fillers, precipitated silica, fumed silica, carbon black, calcium carbonate, titanium oxide, talc and the like are preferred. These fillers may be used singly or two or more kinds of them may be used combinedly. When a filler is used, it is used preferably in an amount of 1 to 500 parts, more preferably 50 to 200 parts, per 100 parts of component (A).
In addition to components (A) to (D) and the above-mentioned plasticizers, solvents, antioxidants, weather-resistant property improving agents and filler, various additives may be added to the primer composition of the present invention as necessary.
As examples of such additives, there may be mentioned physical property modifiers for modifying the tensile characteristics of the resulting cured coats, storage stability improvers, radical inhibitors, metal deactivators, antiozonants, antisagging agents, lubricants, pigments, antifoams and the like.
Specific examples of such additives are described, for example, in Japanese Kokoku Publications Hei-04-69659 and Hei-07-108928, Japanese Patent No. 2512468, and Japanese Kokai Publication Sho-64-22904.
The method of effecting adhesion of a sealing composition to a substrate of the present invention is carried out in the following manner.
At first, the primer composition of the present invention is applied to a substrate and the film formation of the primer composition is performed by standing in a condition according to said primer composition. And then a sealing composition is applied onto the primer layer and cured.
Usable as the sealing composition to be applied onto the primer layer in the present invention are sealing compositions of the modified silicone type, silicone type, polyurethane type, acrylic urethane type, polysulfide type, modified polysulfide type, butyl rubber type, acrylic type, SBR type or fluorine-containing type, for instance, oil-based caulking compounds, silicone-based mastics, and sealing compositions comprising, as the main component, a saturated hydrocarbon polymer having the reactive silicon group, and the like. When used for sealing compositions comprising a saturated hydrocarbon polymer having the reactive silicon group as the main component, among others, the primer composition of the present invention is very effective. In particular, when applied to sealing compositions containing, as the main component, an isobutylene polymer having a reactive silicon group (for example, the isobutylene-based sealing compositions disclosed in Japanese Kokoku Publication Hei-04-69659), said primer composition is preferred because of its good adhesion properties. Further, when using the isobutylene-based sealing compositions having the reactive silicon group, using the isobutylene polymer having a reactive silicon group as the component (A) of the primer is more preferable in consideration of compatibility between the sealing composition and the primer.
The primer composition of the present invention can provide firm adhesion between various metals such as iron, stainless steel, aluminum, nickel, zinc and copper, synthetic resin materials such as acrylic resins, phenol resins, epoxy resins, polycarbonate resins, polybutylene terephthalate resins and alkali-treated fluororesins, inorganic materials such as glass, ceramics, cement and mortar, or cured sealing compositions of the modified silicone type, silicone type, polyurethane type, acrylic urethane type, polysulfide type, modified polysulfide type, butyl rubber type, acrylic type, SBR type, fluorine-containing type or isobutylene type, on one hand, and various sealing compositions on the other.
The primer composition of the present invention can be applied to a substrate using coating techniques generally employed in the art, for example the brushing, spray coating, wirebar, blade, rollcoating, dippingandliketechniques. The primer composition of the present invention can form coat films generally at ordinary temperature. Coat film formation may be effected at various temperature conditions for adjusting the rate of coat formation.